CN102583815A - Method for treating waste liquid produced during on-line chemical oxygen demand (COD) determination with potassium dichromate method - Google Patents
Method for treating waste liquid produced during on-line chemical oxygen demand (COD) determination with potassium dichromate method Download PDFInfo
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- CN102583815A CN102583815A CN2012100196677A CN201210019667A CN102583815A CN 102583815 A CN102583815 A CN 102583815A CN 2012100196677 A CN2012100196677 A CN 2012100196677A CN 201210019667 A CN201210019667 A CN 201210019667A CN 102583815 A CN102583815 A CN 102583815A
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- waste liquid
- potassium dichromate
- cod
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- 239000002699 waste material Substances 0.000 title claims abstract description 78
- 239000007788 liquid Substances 0.000 title claims abstract description 71
- 238000000034 method Methods 0.000 title claims abstract description 43
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 239000000126 substance Substances 0.000 title claims abstract description 7
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title abstract 2
- 239000001301 oxygen Substances 0.000 title abstract 2
- 239000006228 supernatant Substances 0.000 claims abstract description 30
- 239000002904 solvent Substances 0.000 claims abstract description 28
- 150000003839 salts Chemical class 0.000 claims abstract description 24
- 150000002500 ions Chemical class 0.000 claims abstract description 18
- 239000003513 alkali Substances 0.000 claims abstract description 16
- 230000001105 regulatory effect Effects 0.000 claims abstract description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000011734 sodium Substances 0.000 claims description 36
- 230000008569 process Effects 0.000 claims description 24
- 238000002360 preparation method Methods 0.000 claims description 19
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 13
- 229910021645 metal ion Inorganic materials 0.000 claims description 9
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 9
- 235000015320 potassium carbonate Nutrition 0.000 claims description 9
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 9
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 9
- 238000005303 weighing Methods 0.000 claims description 9
- 230000008021 deposition Effects 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 2
- 239000001117 sulphuric acid Substances 0.000 claims description 2
- 235000011149 sulphuric acid Nutrition 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 41
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 14
- 231100000331 toxic Toxicity 0.000 abstract description 6
- 230000002588 toxic effect Effects 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 3
- 150000001875 compounds Chemical class 0.000 abstract description 2
- 230000036541 health Effects 0.000 abstract description 2
- 231100000252 nontoxic Toxicity 0.000 abstract description 2
- 230000003000 nontoxic effect Effects 0.000 abstract description 2
- 238000001556 precipitation Methods 0.000 abstract 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract 1
- 239000001257 hydrogen Substances 0.000 abstract 1
- 229910052739 hydrogen Inorganic materials 0.000 abstract 1
- 239000002244 precipitate Substances 0.000 abstract 1
- 230000036632 reaction speed Effects 0.000 abstract 1
- 239000011651 chromium Substances 0.000 description 34
- 239000000243 solution Substances 0.000 description 20
- 238000003756 stirring Methods 0.000 description 19
- 231100000419 toxicity Toxicity 0.000 description 8
- 230000001988 toxicity Effects 0.000 description 8
- 229910001430 chromium ion Inorganic materials 0.000 description 6
- 239000011259 mixed solution Substances 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 230000003068 static effect Effects 0.000 description 5
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 4
- 239000010808 liquid waste Substances 0.000 description 4
- 238000010561 standard procedure Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 238000007599 discharging Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- 239000004332 silver Substances 0.000 description 3
- 230000002110 toxicologic effect Effects 0.000 description 3
- 231100000027 toxicology Toxicity 0.000 description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 238000012544 monitoring process Methods 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- -1 silver ions Chemical class 0.000 description 2
- DOBUSJIVSSJEDA-UHFFFAOYSA-L 1,3-dioxa-2$l^{6}-thia-4-mercuracyclobutane 2,2-dioxide Chemical compound [Hg+2].[O-]S([O-])(=O)=O DOBUSJIVSSJEDA-UHFFFAOYSA-L 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 240000003864 Ulex europaeus Species 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- LXMQZGGLHVSEBA-UHFFFAOYSA-N chromium;trihydrate Chemical compound O.O.O.[Cr] LXMQZGGLHVSEBA-UHFFFAOYSA-N 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 230000002939 deleterious effect Effects 0.000 description 1
- 230000029087 digestion Effects 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000002920 hazardous waste Substances 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 230000002452 interceptive effect Effects 0.000 description 1
- 238000010297 mechanical methods and process Methods 0.000 description 1
- 230000005226 mechanical processes and functions Effects 0.000 description 1
- 229910000372 mercury(II) sulfate Inorganic materials 0.000 description 1
- 230000009965 odorless effect Effects 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- YPNVIBVEFVRZPJ-UHFFFAOYSA-L silver sulfate Chemical compound [Ag+].[Ag+].[O-]S([O-])(=O)=O YPNVIBVEFVRZPJ-UHFFFAOYSA-L 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Abstract
The invention discloses a method for treating waste liquid produced during on-line chemical oxygen demand (COD) determination with a potassium dichromate method, and belongs to the field of waste liquid treatment. The method is characterized in that a certain proportion of reducing salt is adopted to react with the waste liquid into which an interference removing solvent is added; then alkali is added into the waste liquid and a precipitation reaction is conducted; and finally, the waste liquid stands still to precipitate, and a supernatant can be emitted up to standard after the pH (potential of hydrogen) value is regulated. The method has the advantages as follows: through using the interference removing solvent the utility model effectively solves the problems that high-concentration sulfuric acid in the waste liquid participates in the chemical reactions to produce SO2 to harm the physical health of an operator, and as SO42 minus ions in the waste liquid interferes following chemical reaction steps, the aim of toxic heavy metal removal,; through adding the reducing salt, high-toxic Cr6 plus ions are changed to low-toxic Cr3 plus ions; through adding the alkali, precipitates finally generated in the precipitation reaction only contain non-toxic or low-toxic compounds of the heavy metal; and the reaction speed is high, the whole reaction process can be completed within 5 minutes, and a reaction effect is easy to identify according to color.
Description
Technical field
The present invention relates to a kind of method for treating waste liquid, be specifically related to the method for treating waste liquid that potassium dichromate process on-line determination COD produces.
Background technology
Potassium dichromate process measure COD be consistent mensuration COD standard method of generally acknowledging both at home and abroad at present (NEPA's volume. water and effluent monitoring analytical procedure [M]. the 4th edition. Beijing: environmental science press, 2002,10-213).The principle of measuring is: the mixed solution of water sample, SRM 935a, Sulfuric acid disilver salt and the vitriol oil is heated to 175 ℃ in digestion pool; Chromium ion is reduced the III valency and changes color from the VI valency as oxygenant; The content of organic cpds becomes corresponding relation, COD in the change degree of color and the sample
MaxAnalytical instrument converts through colorimetric and directly the COD in the sample is shown.For avoiding muriatic interference, in mixed solution, add Mercury bisulfate.Therefore, it is high to measure in the waste liquid of COD acidity, and the content of toxic heavy metal mercury, chromium, silver is high.If not treated, directly enter water drain, can cause serious secondary pollution.Especially along with the increasing of environment supervision; Source of pollution on-line monitoring equipment is all actively being installed by various places environmental administration, and current most of import and home-made " COD on line analyzer " all adopt the GB potassium dichromate process to measure COD, and these on line analyzers all do not design the treatment unit of waste liquid; These contain toxic heavy metal ionic discharging of waste liquid in water drain or field environment; Though each amount is little, concentration is higher, accumulates over a long period; Still can cause serious secondary pollution, seem urgent day by day so study the treatment process of this waste liquid.
At present the treatment process of measuring the COD waste liquid is mainly contained 3 kinds, the 1st kind of elder generation considers to be worth doing silver ions (Ag with aluminium
+) with waste liquid in remaining VI valency chromium (Cr
6+) ion generation redox reaction, generate silver-colored simple substance (Ag) and III valency chromium ion (Cr
3+), filtration can obtain silver powder, and the back makes Al with ammoniacal liquor or highly basic sodium hydroxide
3+, Hg
2+, Cr
3+Produce precipitin reaction, thereby obtain white lake (Al (OH)
3), mercuric hydroxide (Hg (OH)
2), chromium hydroxide (Cr (OH)
3) solid (Huang Fengzhen, Zhu Zhiqiang. potassium dichromate process is measured liquid waste disposal and the comprehensive utilization [J] of COD. pollution prevention technique, 2008,3 (21): 94-95); The 2nd kind with silver ions (Ag in the sodium chloride solution removal waste liquid
+), the back makes Cr with alkali
3+, Hg
2+Produce deposition, thus reach the purpose of removing heavy metal ion (Tao Liying. potassium dichromate process is measured COD liquid waste disposal design for scheme [J]. Jinzhou Medical College's journal, 2001,23 (2): 2526); In the 3rd kind of " COD on line analyzer " specification sheets to the treatment process of waste liquid: in the 10L waste liquid, add 30gNaCl, fully stir, make to generate the AgCl deposition, more than the static 12h, inclining in supernatant and the separated liquid supernatant adds 15-20gFeSO
47H
2O is to reduce excessive Cr
6+, fully stir the back and add about 1600gNaOH with the excessive H that neutralizes
2SO
4, regulate the pH value and add 40gNa again for 8-9.
2S9H
2O makes Cr
3+, Fe
3+, co-precipitation such as mercury.After deposition was complete, supernatant directly discharged, and residue is done Hazardous wastes and handled.Find that through test of many times these 3 kinds of treatment process are difficult to transporting in actually operating and commercialization process.Its reason: the 1st kind of the first step speed of response is very slow; Do not consider unnecessary Cr for the 2nd kind
6+Processing, the waste liquid after causing handling is glassy yellow, the heavy metal ion in the waste liquid is handled not thoroughly; The 3rd kind is perfectly in theory, in actual mechanical process because do not consider the influence of other interfering factorss, waste liquid finally all changes solid into, does not reach the result of expectation at all.In addition, the 3rd kind of method reckons without the SO that the vitriol oil is participated in the disturbance reponse generation in the waste liquid
2Gas pollutant.
Summary of the invention
The technical problem that invention will solve
Adopt the problem of the toxic heavy metal ion liquid waste disposal that produces in national standard method (GB/T11914-1989) the on-line measurement COD process to current environmental protection field; And in the prior art to the many disadvantages of liquid waste disposal; The method for treating waste liquid that the present invention provides potassium dichromate process on-line determination COD to produce; Can make the toxic heavy metal ion waste liquid harmless treatment that produces in the national standard method on-line measurement COD process, prevent that secondary pollution from taking place.
.
Technical scheme
Inventive principle: interference with solvent is gone in configuration, goes waste liquid and a certain proportion of reductibility salt hybrid reaction of interference with solvent through adding, with the VI valency chromium ion (Cr in the solution
6+) be reduced into III valency chromium ion (Cr
3+); Go simultaneously interference with solvent, the vitriol oil has been accelerated the reaction in the solution to the interference of subsequent chemical reaction in the elimination waste liquid; Adding a certain proportion of alkali afterwards becomes all heavy metal ion into the precipitable solid of chemical combination attitude and separates out; But supernatant is handled just qualified discharge of back through simple pH, has realized handling fast with effectively of waste liquid, and will be not easy to store to change into transportation, the higher solution of toxicity and be prone to storage and transportation, solid that toxicity is lower.
Technical scheme of the present invention is following:
The method for treating waste liquid that potassium dichromate process on-line determination COD produces the steps include:
(1) interference with solvent is gone in preparation: take by weighing salt of wormwood and sodium hydrogencarbonate, preparation contains K
+, Na
+, HCO
3 -, CO
3 2-Solion, each ionic concn is: K
+: 0.2-0.33g/L, Na
+: 0.11-0.19g/L, HCO
3 -: 0.29-0.50g/L, CO
3 2-: 0.15-0.25g/L, the pH value of solution scope is between 6.5～8.5;
(2) in waste liquid, add the interference with solvent of going that step (1) disposed: go interference with solvent can dilute vitriol oil concentration in the waste liquid, prevent its oxidation-reduction quality salt in step 3, reduced SO in the waste liquid simultaneously
4 2-(Ag
2SO
4, HgSO
4) ionic concentration, avoid it in step 3, to generate vitriol and separate out and disturb Cr
3+, Hg
2+, Ag
+Ion is converted into chemical combination attitude deposition;
(3) reductibility salt is added through in the reacted mixing solutions of step (2): make the strong VI valency chromium ion Cr of remaining toxicity in the waste liquid through adding reductibility salt
6+Be reduced into the low III valency chromium ion Cr of toxicity
3+
(4) will pass through in the pretreated waste liquid of step (3) and add alkali, make Cr
3+, Hg
2+, Ag
+Ion is converted into chemical combination attitude deposition and collects;
(5) reacted supernatant in the step (4) is carried out simple pH and handle, the pH value of regulating supernatant is the 7.0-8.0 qualified discharge.Through detecting, only contain ion in the supernatant, heavy metal Ag to the environment toxicological harmless
+, Hg
2+, Cr
3+, Cr
6+Content is almost nil, well below the index request of national standard.
Wherein, step is gone interference with solvent described in (1), and normal temperature and pressure is the transparent liquid of colorless and odorless down, and cheap easy the acquisition, and to environment toxicological harmless effect, the quality of its adding and waste liquid volume ratio are 1000-5000g:1L in step 2.
The metal ions in waste liquor concentration that potassium dichromate process on-line determination COD described in the step (2) produces is Hg
2+: 1-6.8g/L, Cr
6+: 0-2.83g/L, Cr
3+: 0-2.83g/L, Ag
+: 0.1-2.22g/L.
Reductibility salt described in the step (3) is Na
2SO
3, Na
2S
2O
35H
2O, FeSO
47H
2O, Fe
2(SO
3)
3, FeSO
4, FeCl
2In a kind of or any two or more combination, the quality of its adding with the ratio of the volume of waste liquid is: 0-100g:1L.
Alkali is NaOH or Na in the step 4
2CO
3In a kind of, the quality of its adding with the ratio of the volume of waste liquid is: 10-600g:1L.
The solution of the adjusting supernatant described in the step (5) is a kind of in hydrochloric acid soln or the sulphuric acid soln, and its concentration of volume percent is 10%-30%.
Beneficial effect
The present invention can be fast, comprehensively handle the waste liquid that adopts national standard method on-line determination COD to be produced, and realized will being not easy to store changing into transportation, the higher solution of toxicity being prone to storage and transportation, solid that toxicity is lower.This technology has the following advantages:
(1) the present invention goes interference with solvent through preparation and adding in step 1 and step 2, effectively avoids the vitriol oil of waste liquid middle and high concentration to participate in chemical reaction generation SO
2, harm health of operators, and SO in the waste liquid
4 2-Pair ion step 3, step 4 chemical reaction produce and disturb, and reach the purpose of effective removal toxic heavy metal;
(2) through adding reductibility salt, can be with deleterious VI valency chromium ion (Cr
6+) be reduced into the lower III valency chromium ion (Cr of toxicity
3+);
(3) through adding alkali or alkaline solution, the last throw out that generates of reaction is the very low compound of nontoxic or toxicity that only contains heavy metal, and volume is little, only accounts for 1/5 of overall solution volume, recovery, simple to operate;
(4) speed of response is fast, and entire reaction course can be accomplished in 5min, and reaction effect is easy to discern according to color.
Description of drawings
Fig. 1 is a technological principle schema of the present invention.
Among the figure: the first step goes the waste liquid of interference with solvent and the reductibility salts solution of corresponding proportion to react 1 adding; On reaction 1 basis, add alkali afterwards and react 2; These two reactions are all accomplished in several minutes, and the mixed solution that reaction 3 will be reacted 2 generations staticly settles, by the time behind the precipitated and separated; Add dilute acid soln in the process that supernatant is discharged and carry out the pH regulator processing, last qualified discharge.The throw out that reaction 2 is produced carries out press filtration or air-dry, forms the solid mud cake that contains heavy metal ion, and the unit that delivers to qualification after the centralized collection handles.
Embodiment
Embodiment 1:
In reactor drum, add the 1L waste liquid, metal ions in waste liquor concentration is Hg
2+: 1g/L, Cr
3+: 2.83g/L, Ag
+: 0.1g/L; Interference with solvent is gone in preparation: take by weighing salt of wormwood and sodium hydrogencarbonate, preparation contains K
+, Na
+, HCO
3 -, CO
3 2-Solion 5000g, each ionic concn is: K
+: 0.2g/L, Na
+: 0.11g/L, HCO
3 -: 0.29g/L, CO
3 2-: 0.15g/L, the pH value of solution scope is between 6.5～8.5; In waste liquid, add the 5000g that is disposed and go interference with solvent, to wherein adding 0g reductibility salt, at this moment, do not contain Cr in the waste liquid again
6+Ion only contains Cr
3+Ion, stirring reaction, reaction in about 2 minutes finishes;
In reactor drum, add 10g alkali again, the kind of alkali is NaOH or Na
2CO
3In any one, behind the stirring reaction, reaction in about about 3 minutes finishes;
Static placement, the supernatant of draining adds 10% Hydrogen chloride supernatant is carried out simple pH processing, and the pH value of regulating supernatant is 7.0-8.0, collects settling simultaneously.
Embodiment 2:
In reactor drum, add the 1L waste liquid, metal ions in waste liquor concentration is Hg
2+: 6.8g/L, Cr
6+: 2.83g/L, Cr
3+: 0g/L, Ag
+: 2.22g/L; Interference with solvent is gone in preparation: take by weighing salt of wormwood and sodium hydrogencarbonate, preparation contains K
+, Na
+, HCO
3 -, CO
3 2-Solion 1000g, each ionic concn is: K
+: 0.28g/L, Na
+: 0.15g/L, HCO
3 -: 0.40g/L, CO
3 2-: 0.22g/L, the pH value of solution scope is between 6.5～8.5; In waste liquid, add the 1000g that is disposed and go interference with solvent, to wherein adding 60g reductibility salt, reductibility salt is Na again
2SO
330g, Na
2S
2O
35H
2The O30g stirring reaction, reaction in about 2 minutes finishes;
In reactor drum, add 480g alkali again, the kind of alkali is NaOH or Na
2CO
3In any one, behind the stirring reaction, reaction in about about 3 minutes finishes;
Static placement, the supernatant of draining, adding concentration of volume percent is 30% hydrochloric acid, supernatant is carried out simple pH handle, the pH value of regulating supernatant is 7.0-8.0, collects settling simultaneously.
Embodiment 3:
In reactor drum, add the 1L waste liquid, metal ions in waste liquor concentration is Hg
2+: 2.8g/L, Cr
6+: 1.83g/L, Cr
3+: 1.0g/L, Ag
+: 1.22g/L; Interference with solvent is gone in preparation: take by weighing salt of wormwood and sodium hydrogencarbonate, preparation contains K
+, Na
+, HCO
3 -, CO
3 2-Solion 3000g, each ionic concn is: K
+: 0.33g/L, Na
+: 0.19g/L, HCO
3 -: 0.50g/L, CO
3 2-: 0.25g/L,, the pH value of solution scope is between 6.5～8.5; In waste liquid, add the 3000g that is disposed and go interference with solvent, again to wherein adding 100g reductibility salt, reductibility salt FeSO
47H
2O is 20g, Fe
2(SO
3)
3Be 20g, FeSO
4Be 30g, FeCl
2Be the 30g stirring reaction, reaction in about 2 minutes finishes;
In reactor drum, add 480g alkali again, the kind of alkali is NaOH or Na
2CO
3In any one, behind the stirring reaction, reaction in about about 3 minutes finishes;
Static placement, the supernatant of draining, adding concentration of volume percent is 10% hydrochloric acid, supernatant is carried out simple pH handle, the pH value of regulating supernatant is 7.0-8.0, collects settling simultaneously.
Embodiment 4:
In reactor drum, add the 1L waste liquid, metal ions in waste liquor concentration is Hg
2+: 3g/L, Cr
6+: 2.83g/L, Ag
+: 1.0g/L; Interference with solvent is gone in preparation: take by weighing salt of wormwood and sodium hydrogencarbonate, preparation contains K
+, Na
+, HCO
3 -, CO
3 2-Solion 3000g, each ionic concn is: K
+: 0.33g/L, Na
+: 0.19g/L, HCO
3 -: 0.50g/L, CO
3 2-: 0.25g/L, the pH value of solution scope is between 6.5～8.5; In waste liquid, add and remove interference with solvent 3000g, in waste liquid, add 60g reductibility salt again, reductibility salt is Na
2SO
3Be 10g, Na
2S
2O
35H
2O is 10g, FeSO
47H
2O is 20g, FeSO
4Be 10g, FeCl
2Behind the 10g stirring reaction, reaction in about 2 minutes finishes;
In reactor drum, add 480gNaOH again, behind the stirring reaction, reaction in about about 3 minutes finishes;
Static placement, the supernatant of draining, adding concentration of volume percent is 30% sulfuric acid, supernatant is carried out simple pH handle, the pH value of regulating supernatant is 7.0-8.0, collects settling simultaneously.
Embodiment 5:
In reactor drum, add the 1L waste liquid, fully stir waste liquid with pneumatic pump, metal ions in waste liquor concentration is Hg
2+: 6.8g/L, Cr
6+: 2.83g/L, Ag
+: 2.22g/L; Interference with solvent is gone in preparation: take by weighing salt of wormwood and sodium hydrogencarbonate, preparation contains K
+, Na
+, HCO
3 -, CO
3 2-Solion 2500g, each ionic concn is: K
+: 0.26g/L, Na
+: 0.16g/L, HCO
3 -: 0.42g/L, CO
3 2-: 0.20g/L, the pH value of solution scope is between 6.5～8.5; , the pH value of solution scope is between 6.5～8.5; Go interference with solvent to wherein adding 2500g, again to adding 100g reductibility salt, reductibility salt Na
2SO
3Be 10g, Na
2S
2O
35H
2O is 40g, FeSO
47H
2O is 40g, FeSO
4Behind the 10g stirring reaction, reaction in about 2 minutes finishes;
Pneumatic pump continues to stir, and in reactor drum, adds 600gNaOH again;
Stop air agitator, mixed solution is discharged to a bigger container, leave standstill, supernatant is discharged in another container, and the use concentration of volume percent is to discharge the collection settling behind the 20% sulfuric acid adjusting pH to 7.0-8.0.
Embodiment 6:
In reactor drum, add the 1L waste liquid, fully stir waste liquid with pneumatic pump, metal ions in waste liquor concentration is Hg
2+: 3.0g/L, Cr
6+: 2.0g/L, Cr
3+: 0.83g/L, Ag
+: 2.22g/L; Interference with solvent is gone in preparation: take by weighing salt of wormwood and sodium hydrogencarbonate, preparation contains K
+, Na
+, HCO
3 -, CO
3 2-Solion 5000g, each ionic concn is: K
+: 0.33g/L, Na
+: 0.19g/L, HCO
3 -: 0.50g/L, CO
3 2-: 0.25g/L, the pH value of solution scope is between 6.5～8.5; , the pH value of solution scope is between 6.5～8.5; Go interference with solvent to wherein adding 5000g, to adding 100g reductibility salt, reductibility salt is Na again
2SO
3Be Na
2S
2O
35H
2O is 10g, FeSO
47H
2O is 50g, FeSO
4Behind the 40g stirring reaction, reaction in about 2 minutes finishes;
Pneumatic pump continues to stir, and in reactor drum, adds 600gNa again
2CO
3
Stop air agitator, mixed solution is discharged to a bigger container, leave standstill, the discharging supernatant is to another container, and using concentration of volume percent is that 20% hydrochloric acid is regulated pH to 7.0-8.0, and qualified discharge is collected settling.
Embodiment 7:
In reactor drum, add the 1L waste liquid, fully stir waste liquid with pneumatic pump, metal ions in waste liquor concentration is Hg
2+: 3.0g/L, Cr
6+: 0.83g/L, Cr
3+: 0.20 g/L, Ag
+: 2.22g/L; Interference with solvent is gone in preparation: take by weighing salt of wormwood and sodium hydrogencarbonate, preparation contains K
+, Na
+, HCO
3 -, CO
3 2-Solion 1000g, each ionic concn is: K
+: 0.33g/L, Na
+: 0.19g/L, HCO
3 -: 0.50g/L, CO
3 2-: 0.25g/L, the pH value of solution scope is between 6.5～8.5; The pH value of solution scope is between 6.5～8.5; Go interference with solvent to wherein adding 1000g, to adding 100g reductibility salt, reductibility salt is Na again
2S
2O
35H
2After O was the 100g stirring reaction, reaction in about 2 minutes finished; Pneumatic pump continues to stir, and in reactor drum, adds 600gNaOH again; Stop air agitator, mixed solution is discharged to a bigger container, leave standstill, using concentration of volume percent in discharging supernatant to another container is that 30% hydrochloric acid is regulated pH to 7.0-8.0, and qualified discharge is collected settling.
Embodiment 1-7 supernatant only contains the ion to the environment toxicological harmless, heavy metal Ag through detecting in the supernatant
+, Hg
2+, Cr
3+, Cr
6+Content is almost nil, well below the index request of national standard.
Claims (6)
1. the method for treating waste liquid of potassium dichromate process on-line determination COD generation the steps include:
(1) interference with solvent is gone in preparation: take by weighing salt of wormwood and sodium hydrogencarbonate, preparation contains K
+, Na
+, HCO
3 -, CO
3 2-Solion, each ionic concn is: K
+: 0.2-0.33g/L, Na
+: 0.11-0.19g/L, HCO
3 -: 0.29-0.50g/L, CO
3 2-: 0.15-0.25g/L, the pH value of solution scope is between 6.5～8.5;
(2) in waste liquid, add the interference with solvent of going that step 1 disposed;
(3) reductibility salt is added through in the reacted mixing solutions of step 2;
(4) will pass through in the pretreated waste liquid of step 3 and add alkali, make Cr
3+, Hg
2+, Ag
+Ion is converted into chemical combination attitude deposition and collects;
(5) reacted supernatant in the step 4 is carried out simple pH and handle, the pH value of regulating supernatant is 7.0-8.0.
2. the method for treating waste liquid that produces according to claim 1 potassium dichromate process on-line determination COD is characterized in that go interference with solvent in the said step 2, the quality of its adding and waste liquid volume ratio are 1000-5000g:1L.
3. the method for treating waste liquid that produces according to claim 2 potassium dichromate process on-line determination COD is characterized in that, the metal ions in waste liquor concentration that potassium dichromate process on-line determination COD produces in the said step 2 is Hg
2+: 1-6.8g/L, Cr
6+: 0-2.83g/L, Cr
3+: 0-2.83g/L, Ag
+: 0.1-2.22g/L.
4. the method for treating waste liquid that produces according to claim 3 potassium dichromate process on-line determination COD is characterized in that the reductibility salt described in the said step 3 is Na
2SO
3, Na
2S
2O
35H
2O, FeSO
47H
2O, Fe
2(SO
3)
3, FeSO
4, FeCl
2In a kind of or any two or more combination, the quality of its adding with the ratio of the volume of waste liquid is: 0-100g:1L.
5. the method for treating waste liquid that produces according to claim 4 potassium dichromate process on-line determination COD is characterized in that alkali is NaOH or Na in the said step 4
2CO
3, the quality of its adding with the ratio of the volume of waste liquid is: 10-600g:1L.
6. the method for treating waste liquid that produces according to claim 5 potassium dichromate process on-line determination COD is characterized in that, the solution of regulating supernatant in the said step 5 is a kind of in hydrochloric acid soln or the sulphuric acid soln, and its concentration of volume percent is 10%-30%.
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| CN103288231A (en) * | 2013-04-16 | 2013-09-11 | 山东益源环保科技有限公司 | Industrial treatment process for CODCr waste liquid |
| CN103864196A (en) * | 2014-03-19 | 2014-06-18 | 上海摩威环境科技股份有限公司 | Treatment method for waste liquid produced by permanganate titration COD (chemical oxygen demand) online determination instrument |
| CN105417825A (en) * | 2015-12-28 | 2016-03-23 | 河北科瑞达仪器科技股份有限公司 | Waste liquid flash evaporation treatment method |
| CN105588927A (en) * | 2014-11-14 | 2016-05-18 | 株式会社岛津制作所 | Treatment method for waste liquid in COD measurement apparatus |
| CN106630298A (en) * | 2017-01-19 | 2017-05-10 | 天津碧水源膜材料有限公司 | Method for rapidly treating Ag<+>, Cr<6+> and Hg<2+> in industrial acidic waste liquid |
| CN108956853A (en) * | 2018-07-16 | 2018-12-07 | 郑州市通标环境检测有限公司 | A kind of method that dichromate titration measures COD in water |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103288231A (en) * | 2013-04-16 | 2013-09-11 | 山东益源环保科技有限公司 | Industrial treatment process for CODCr waste liquid |
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| CN106630298A (en) * | 2017-01-19 | 2017-05-10 | 天津碧水源膜材料有限公司 | Method for rapidly treating Ag<+>, Cr<6+> and Hg<2+> in industrial acidic waste liquid |
| CN108956853A (en) * | 2018-07-16 | 2018-12-07 | 郑州市通标环境检测有限公司 | A kind of method that dichromate titration measures COD in water |
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